Amine-epoxide compositions



United States Patent" 2,865,888 AMINE-EPOXIDE COMPOSITIONS Sylvan Owen Greenlee, Racine, Wis., assignor to Devoe & Raynolds Company, Inc, Louisville, Ky., a corporation of New York No Drawing. Original application Serial No. 271,069. Divided and this application August 22, 1957, Serial No. 679,755

8 Claims. c1. 260-47) February 11, 1952,

infusible products, and valuable for use in making varnishes and protective coatings, in making molding compositions and articles, as adhesives, and in making films and fibres, etc. The invention includes new hexamethylcne diamine-epoxy compositions and reaction products and articles and products made therefrom.

The new hexarnethylene diamine-epoxy compositions and products are made by reacting hexamethylene diamine with complex epoxides produced by the reaction containing terminal epoxide groups. Such epoxide products with which the amine is reacted are advantageously complex polymeric products resulting from the rein my'companion applications Serial No. 617,176, filed September 18, 1945 (now abandoned), Serial No. 621,856, filed October 11, 1945 (now abandoned), and Serial No. 626,449, filed November 2, 1945, now Patent No. 2,592,560.

One of the objects of the present invention is the production of infusible and insoluble reaction products of other desirable properties.

Another object of the invention isthe production of solutions of such hexamethylene diamine-epoxy compositions for use in making varnishes and protective coatings, impregnating solutions, films, filaments, etc;

' 2,865,888 Patented Dec. 23, 1958 Other objects of the invention and the nature and advantages of the invention will further appear from the following more detailed description.

In my companion application Serial No. 617,176, filed September 18, 1945 (now abandoned), I have described complex, polymeric reaction products of polyhydric phenols with polyfunctional halohydrins such as epichlorhydrin and glycerol dichlorhydrin, with the difunctional chlorhydrin used in proportions in excess of to the polyhydric phenol and less than twice the equivalent amount, by carrying out the readdition of caustic alkali equal to or somewhat in excess of the amount required to combine with the halogen of the halohydrin and giving complex, polymeric products containing both terminal epoxy groups and terminal primary hydroxyl groups, and with the epoxy groups in general considerably in excess of the terminal primary hydroxyl groups. Such complex, polymeric epoxyhydroxy products and compositions are advantageously used for reaction with hexamethylene diamine to form the new amine epoxy compositions and products of the present invention.

In my companion application Serial No. October 11, 1945 (now abandoned), I have described epoxy-hydroxy compositions resulting from the reaction of a polyhydric phenol with a polyfunctional halohydrin such as epichlorhydrin in approximate proportions of 2 mols of epichlorhydrin to one of dihydric phenol to give resinous products containing both terminal epoxy and hydroxy groups with the proportion of terminal epoxy groups considerably in'excess of the terminal hydroxy groups. Such epoxy-hydroxy compositions are also advantageously used in forming the new hexamethylene diamine-epoxy compositions and products of the present invention.

In my companion application Serial No. 626,449, filed November 2, 1945, noW Patent No. 2,592,560, I have described new polyepoxy products and compositions obtained by the direct addition of polyhydric phenols with polyepoxides and with the proportion of poly- 621,856, filed products will contain terminal epoxy groups. Such polyepoxy reaction products, and particularly complex polyseparated from each other by hydrocarbon groups and enable the amine to react with a number of epoxide groups with resulting cross-linking to give complex amineepoxy reaction products.

Fusiblehexamethylene diarnine-epoxy reaction prod ucts can be prepared with limited amounts of hexamethylene diamine under proper reaction conditions. The maximum complexity of hexamethylene diamine-epoxy re'actionproducts appears to be obtained when hexa:

the hexamethylene diamine.

' harder resins of higher melting point.

controlled to some extent otherwise than by adjusting the ratio of hexamethylene diamine and epoxy reactants, as by using moderate reaction conditions such as lower temperatures or shorter reaction periods or both, to give fusible products which are Valuable intermediate products and which may, if the hexamethylene diamine and epoxide are only partially reacted and are in proper proportions for further reaction, give infusible products when subjected to such further reaction or conversion.

The complex epoxide compositions used with the hexamethylene diamine are themselves capable of polymerization by reaction of epoxy groups with hydroxyl groups, particularly in the presence of small amounts of a catalyst. The complex epoxy compositions made from polyhydric phenols and epichlorohydrin contain both terminal epoxy groups and terminal primary hydroxyl groups and, in general, the number of terminal epoxy groups is considerably in excess of the number of terminal primary hydroxyl groups. In polymeric products containing intermediate hydroxyl groups, the total number of hydroxyl groups may be considerably in excess of the number of epoxy groups. Polymerization of such complex epoxyhydroxy compounds may take place through terminal epoxy and primary hydroxyl groups to form long chain polymers or through terminal epoxy groups and intermediate hydroxyl groups to form polydimensional polymers.

In the case of polyepoxides made by the direct reaction of bisphenol with an excess of polyepoxide there will also be hydroxyl groups, and, in the case of polymeric products, the number of hydroxyl groups may be in excess of the terminal epoxy groups. Such products are capable of polymerization by reaction of terminal epoxide groups with intermediate hydroxyl groups to form complex, polydimensional polymers, particularly when a catalyst is used.

When such complex epoxide compositions are reacted with hexamethylene diamine, the action of the amine may be one of direct addition through epoxide groups and it may be in part a catalytic action promoting the combination of epoxy and hydroxyl groups to form ether linkages, particularly where the hexamethylene diamine is used in less than equivalent proportion such that there is insufiicienut amine to react with all of the epoxide groups.

The complex epoxide compositions which are reacted with the hexamethylene diamine are resinous products which can be made of varying melting points, epoxide content, and degree of polymerization from soft resins to In general, these resins are soluble, unless too highly polymerized, in sol vents such as acetone, methyl ethyl ketone, diacetone alcohol, cyclohexanone, etc. and can be used in solution with the addition of hexamethylene diamine in forming liquid compositions for use e. g. in making clear or pigmented varnishes, in making transparent films and filaments, and in impregnating wood, fabrics and other porous material, etc.

The reaction of hexamethylene diamine with such complex epoxides appears to be one of cross-linking the complex epoxide molecules through reaction of the hexaniethylene diamine with epoxide groups. But such crosslinking reaction may be: combined with a simultaneous polymerization reaction between epoxide and hydroxyl groups, particularly when the amine is used in less than equivalent proportion.

When polyepoxides are reacted with the hexamethylene diamine and where the polyepoxides contain only or mainly terminal epoxide groups with intermediate hydroxyl groups, the action of the hexamethylene diamine is such that considerably less than the equivalent amount of hexamethylene diamine will react with the polyepoxide to form 'infusible products; while the epoxide groups which are present in excess of those reacting with the hexamethylene diamine may react to a greater or less extent with hydroxyl groups, in which case the complex 4 epoxy-hexamethylene diamine reaction products may have the polyepox'ides united in part through amine cross-linking and in part through epoxy-hydroxide reaction to form ether linkages.

Similarly in the case of the complex polymeric epoxides which also contain terminal hydroxyl groups, the final hardening operation, particularly when less than the equivalent amount of hexamethylene diamine is used, may be in part cross-linking through the amine and in part by polymerization through epoxy-hydroxy reactions to form ether linkages.

The complex epoxides and polyepoxides used for reacting with the amines may themselves be carried to a high degree of polymerization in which case only a small amount of hexamethylene diamine may be necessary to convert the highly polymerized epoxides into an infusible state. With products of lower melting point and lower degree of polymerization an increased amount of crosslinking or polymerization in the presence of the amine, a large proportion of amine may be necessary to give the final insoluble product.

in referring to equivalent amounts of hexamethylene diamine and of the complex polyepoxides, each active hydrogen attached to nitrogen of the amine is considered equivalent to one epoxide group. The equivalent weight of the hexamethylene diamine is the weight which will contain one such active amine hydrogen when used with an equivalent weight of the complex epoxides containing one epoxide group.

In referring to equivalent amounts of hexamethylene diamine, or to less than equivalent amounts, the amounts are those used with the complex epoxides, and it is not intended to mean that the amount used is completely reacted. While theoretically complete reaction might take place it is probable that the reaction is a partial and incomplete reaction between part of the active hydrogens of the hexamethylene diamine and the epoxide groups.

The epoxide equivalent of the complex epoxides used can be determined for practical purposes by determining the equivalent weight of the composition per epoxide group.

The epoxide content of the epoxide-hydroxy compositions hereinafter indicated were determined by heating a 1 gram sample of the epoxide composition with an excess of pyridine containing pyridine hydrochloride (made by adding 16 cc. of concentrated hydrochloric acid per liter of pyridine) at the boiling point for 20 minutes and back titrating the excess pyridine-hydrochloride with 0.1N sodium hydroxide using phenolphthalein as indicator, and considering that 1 HCl is equal to 1 epoxide group.

Example One-halt of the equivalent of hexamethylene diamine (15 parts by weight) was mixed with a hydroxy-epoxy composition resulting from the reaction of bisphenol with epichlorhydrin with the use of caustic soda according to said companion applications having a softening point of C. an equivalent weight to epoxide of 860 and an average molecular weight of 1133. The mixture was then heated for 30 minutes at C. The resulting product was infusible and possessed the properties and advantages herein set forth.

In a similar manner other complex epoxides made from other polyhydric phenols with epichlorhydrin can be similarly treated to give infusible products or fusible resins the amount of hexamethylene diamine required varying somewhat with difierent epoxides.

In a similar manner complex polyepoxides can be similarly compounded with different proportions of hexamethylene diamine to give infusible products or fusible products depending upon the proportions of hexamethylene diamine used and upon the particular polyepoxy composition employed for reaction therewith! While the example given above includes heating of the hexamethylene diamine-epoxide composition to bring' about the reaction, it is also possible ersion of the epoxide resins It is a characteristic of such films that the reaction of the hexamethylene diamine with the epoxide resin ble desirable properties.

The new compositions are also valuable for use in making molded objects, where the conversion forms infusible, molded products. They are also valuable for use in impregnating and laminating wood and fabrics, in making self-sustaining films and filaments, etc. It has been observed that films will harden even when immersed in water.

Infusible products produced from the new hexamethylene diamine-epoxy compositions have been found to have extreme chemical stability. Varnish films prepared from several of these compositions were unaffected by immersion in 50% H 50 for one hour. Such films when immersed in boiling acetone (56.1" C.) for one hour nail while in the boiling acetone; however, such films quickly returned to their original glossy hardness upon removal from the boiling acetone and apparently little or no solution had occurred.

The infusible films show remarkable stability to caustic alkali. Films immersed in 50% aqueous sodium hydroxide and kept in a sealed bomb in an oven at 100 for one week, and similar tests using 5% aqueous sodium hydroxide, gave no observable effect from such treatment films. Such films are suitable as liners for food and processing equipment for many industrial uses. Such properties also make the new compositions valuable as forming compositions for application over alkaline cement and alkaline plastering surfaces.

Molded objects and films formed from the infusible products of the present invention have extremely hard,

flexibility must be sacrificed; but the insoluble films of the present invention combine hardness with flexibility.

As an indication of the hardness and flexibility of the films made by the reaction of amines with the complex epoxides, extremely hard, infusible films abled ribbons of indefinite length to be stripped from a film from one to two mils thickness by the use of a sharp knife blade.

on glass en- 7 sired amount of gloss,

Such films remain surprisingly flexible atsub-zero temperatures. Varnish films prepared from these compositions have been tested at C. and showed ibility. In general physical toughness and structure the infusible hexamethylene diamine-epoxy resins are comparable to fingernail and horn.

When molded objects are formed by converting a mix ture of the epoxy and hexamethylene diamine in a mold epoxide groups through reaction with amine or the opening up of epoxide groups through reaction with hydroxyl groups to form ether linkages tends to cause separation of the reacting molecules instead of contraction which is characteristic of many condensation polymerization reactions.

This lack of contraction or slight expansion in the mold is highly valuable for many applications, enabling tight fitting molded articles to be obtained. For example, brushes of many types are made by using a If the resin contracts during heat conversion the molded material becomes loose fitting in the ferrule. The new epoxide-amine resins and compositions of the present invention give a tight fitting mold within the brush fer- Similarly molded inserts can be made composition is hardened in place.

The new infusible epoxide-hexamethylene diamine reaction products give extremely glossy films when used as clear or as pigmented enamels. This is highly desirable in the protective coating industry to obtain the desince it is often impossible to obtain such gloss when known vehicles are used.

The new amine-epoxide compositions may be pigmented with the usual pigments known to the protective coating industry to give enamels. The epoxide may be pigmented either before or after the amine is added.

The new epoxide-hexamethylene diamine reaction prod- The new epoxy-hexamethylene diamine compositions and violet light (minimum ultraviolet absorption); extreme alkali with very low sistance to chemicals; insolubility to solvents; non-yellow-' ing; ability to stand temperatures up to 400 F. with little or no discoloration; wettability to most pigments;

low viscosity at high solids content of solutions; and hardening of thick films through chemical addition reactions within the film itself so that paint and varnish coatings far beyond the usual thickness can be applied.

These remarkable properties and combinations of properties make the new compositions, and products made therefrom, valuable for many practical purposes. No other materials so far as I am aware possess so many of the features desired for protective coatings, molded objects, films, filaments, etc.

This application is a division of my prior application Serial No. 271,069, filed February 11, 1952, which application is in turn a continuation-in-part of my prior application Serial No. 617,177, filed September 18, 1945, now Patent No. 2,585,115.

I claim:

1. A composition of matter which is capable of hardening which comprises an unreacted mixture of normally solid resinous glycidyl polyethers of a polyhydric phenol and hexamethylene diamine.

2. A composition of matter which is capable of hardening which comprises an unreacted mixture of normally solid complex resinous epoxides and hexamethylene diamine, said complex resinous epoxides being polymeric polyethers of dihydric phenols, said dihydric phenols being free from functional groups other than phenolic hydroxyl groups, said resinous epoxide resulting from. the heating of the dihydric phenol with an excess of epichlorhydrin with caustic alkali and having intermediate alcoholic hydroxyl-containing aliphatic groups and epoxidecontaining terminal aliphatic groups, said resinous epoxide being free from functional groups other than alcoholic hydroxyl and epoxide groups, and the amount of hexamethylene diamine being from about .25 to 1.7 of the amount equivalent to the resinous epoxide, considering one active hydrogen of the amine groups equivalent to one epoxide group of the complex epoxide,

3. The heat reaction product of the composition of matter of claim 1.

4. The heat reaction product of the composition of epoxides resulting from the heating of the dihydric phenol with an excess of epichlorhydrin and of caustic alkali and having intermediate alcoholic hydroxyl-containing aliphatic groups and epoxide-containing terminal aliphatic groups, said resinous epoxides being free from functional groups other than alcoholic hydroxyl and epoxide groups, and the amount of hexamethylene diamine being from about .25 to about 1.7 of the amount equivalent to the resinous epoxide, considering one active hydrogen of the amine groups of the polyamine equivalent to one epoxide group of the complex epoxide, and molding said mixture with the application of heat to form an insoluble, infusible molded product.

6. The process according to claim 5 in which the resinous epoxide is a polymeric polyether of dihydroxydiphenyldimethyl methane.

7. Molded articles produced by the process of claim 5.

8. Molded articles produced by the process of claim 6.

References Cited in the file of this patent UNITED STATES PATENTS Certificate of Correction Patent N 0. 2,865,888 December 23, 1958 Sylvan Owen Grcenlee It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 1, line 45, for concentration read -contractionbeiore polymerization insert -and-.

Signed and sealed this 28th day of April 1959.

; column 6, line 18,

[SEAL] Attest T. B. MORROW,

ROBERT C. WATSON, Attestz'ng 07720212 Commissioner of Patents. 

1. A COMPOSITION OF MATTER WHICH IS CAPABLE OF HARDENING WHICH COMPRISES AN UNREACTED MIXTURE OF NORMALLY SOLID RESINOUS GLYCIDYL POLYETHERS OF A POLYHYDRIC PHENOL AND HEXAMETHYLENE DIAMINE. 